Method for reforming materials and product thereof



icity.

' Patented Nov. 21, 1944 METHOD FOR REFORMING MATERIALS AND PRODUCT THEREOF Jacquelin ErHfllVBY, In; Washington, D. (7., and Robert H-Whitfi, Jr., and Joseph A.'Vaughan, Atlanta, .Ga., rassignors of one-hall to said Harvey, Jr., and one-half to Southern -Wood -Preserving Company, East Point, Ga.,.a corpo-.

ration of Georgia No Drawing. *Application December 21,.19tl2r";

Serial No. 469,720

21 Claims. (01; 196-53) The instant invention relates to the production of toxic oils employable as fungicides, insecti cities, and for any other service to which toxic oils may be put. a

More especially the instant invention relates to the production of toxic oils from mixtures of petroleum fractions characterized by ring structure content.

may be mentionedmixturesof petroleumfrac- Among such starting materials tions characterized'by ring structurecontent'recovered from petroleum fractions by Well known extraction methods including extractive distillation and azeotropic distillation. Alsdmay be mentioned mixtures of petroleum fractions char acteri'z'ed by ring structure content as flowing from thermal and/or catalytic treatment' of certain petroleum fractions which includes petroleum fractions having ring structures induced in the course of thermal and/or catalytic treatment,

as for example having ring structures induced in the course of one or morethermal and/or catalytic treatments of unusual length; as for exam-. pie, for periods or from 1-10hours or more.

An objectofthe instant invention is theproduction of toxic oils from the aforenamed 25 i d-w The net result of this situation-obtaining is that the coal tar distiller usually conpetroleumfractions or others whereby to pro vide oils of the preservative type, as for example preservative wood impregna'nts .conformingto specifications extant or acceptable to the trade consuming such oil materials. a

Another object of the instant invention is the provision of preservative wood impregnants having boiling ranges and residues inaccordance with published specifications and/or in accordance with consumer preference.

Another object of the instant invention isthe reforming, modifying, converting and/or .trans forming of the mixtures of hydrocarbons where by to induce toxicity, 5 a

, Still another object of the instant invention is 40 4 0 S etaN W o city, o e the Franklin Institute; Philadelphia, Pennsylvania, in

December, 1932, The economics of coal'tar have the induction of usable toxicity in thepresence offa gas or Ygaseous mixtures. V a h Another, object of the-instant invention isthe unveiling of latent toxicity in mixtures ofpetroleumfractions having inherent but inhibitedtox- Anotherobject .ot'the instant invention is the induction of toxicity in the presence of catalytic materials adaptedto favorably influence said toxicity induction.

In the past woodpreservative oils of the high temperature coal tar derived type have beenemployedin quantities greatly exceeding the total of all other wood "preservative oils. standpoint ofavailability of said coal tar as the parent product of wood preservative oils, it is annually produced in this country under normal conditions to the extent of five hundred million to six hundred million gallons. This quantity of 1 coal tar is capable of yielding. an amount of 5 highly effective wood preservative oil which would make this country self-sufficient in its wood preservativerequirements. However, due to the fact that when a, wood preservative distillate (creosote) is recovered from coal tar there, remains in the still a residue (pitch) which, at .best, is a low priced product and which, at worst} is a seriously distress product to the end thatat times it is placed in inventory rather'than sold, the

current method of ,distilling tar leaves much to fines himself to that distillation recoveryof creo- 1 a sote which would correspond to the attending amount of pitch that he canmarket ata profit. Accordingly, over aperiod of years several hundred million gallons of creosote oil-have been importedinto this country. That'such asituation shouldobtain is apparently a paradox in that'we annually produce a quantity of high temperature coal tar which if processed to yield creosotewould dress given by nolless anauthority than S. P..

Miller, technicaljdirector, The Barrettcompany.

not materially changed since that date f. ..In view oftheapparent inabilityof the coal tar a 4-5 industry to; provide-.national needs of wood preservative oils, a strong incentive is given to groups From the Another object of theinstant invention is .the coordination of process variablesso as toprovide specific gravities within definite limits invarious fractionsof the beneficiated material.

qprocessingothentypes ofoil to invade the lucra- V .tivegwood preservative marketwAt the present time manygtypesof aromatic oils are produced by the wpetroleumfindustry, and the .highbolling Martin Closed Cup; 0.

example monocyclic and polycyclic naphthenes.

The so-called petroleum aromatics which includes the monocyclic and polycyclic naphthenes and unsaturated hydrocarbon fractions have in the past been produced in very large quantities. However, very little work has been done on these materials. Such a fact is borne out on page 667,

"Reactions of pure hydrocarbons," Gustav Egloff,

Reinhold Publishing Corporation, 330 West 42nd Street, New York city, which states:

Despite the fact that naphthenes or cycloparaflines are. available in enormous quantities,

, as shown by an estimate Of 100,000,000 barrels present in the 1,498,000,000 barrels of crude oil which was the world's production in 1934, comparatively little work of a pyrolytic nature has been performed on individual naphthene hydro carbons or the cycloolefins.

Several oils of cyclic content produced by the petroleum industry have been inspected for their toxicity to wood destroying fungi, among which 1 may be mentioned a high boiling oil of cyclic content produced (1940) at the Wood River Refinery of the Shell Oil Company and which has the following inspection:

1 Maximum. In the foregoing tabular data P'. M. C.'C. means Pensky- 0. C. means Cleveland Open Cup.-

Upon evaluating the foregoing oil for its toxicity to wood destroying'fungi (Madison 517), it was found that this oil did not inhibit the growth of the fungi named at a concentration-of up to and including 10%.

' vention.

According to the instant'invention oils ofcyclic content produced by the petroleum industry are reformed, transformed, modified and/or converted tooils-of a more toxic nature having characteristics acceptable to consumers of wood preservative impregnant and/or conforming to wood preservative specifications extant.

It is a specific object of the instant invention to reform, transform, modify and/r convert mixtures of petroleum fractions characterized by cyclic structures having inherent but inhibited toxic properties in the vapor phase in the presence of added gas or gases,with or without catalysts, to materials exhibiting a more pronounced toxicity than the parent feed stock.

In former attempts to provide a wood preserva- Oil, Distillation per cent s. 9. 2 9 QFOOQ cellulosic materials to be preserved is entirely too volatile to provide an acceptable preservative im- Gravity 10.8 Flash, P. M. C. C -l -F 295 Flash, C. O. C F 290 Fixed carbon -per cent 4.9 Pour point -l F -10 B. S. 8: W- per cent by volume 0.1

- S. U. vis. 100 F 'l 151 S. U. vis'. 210 F; 41 S. F. vis. 77 F 34.5 Carbon 'residue 6.8 Per cent aromatic and unsaturates 82.4

' S0]. in CS2 99.8 Loss 50 grams,'5 hours, '325 F 8.9 Residue of 100 pene per cent 37.5 A. S. T. M. distillation:

'I. B. P -F 518 10% Rec. F 565 Rec. F 589 Rec. "F 614 Rec. F c 637 Rec. "F 660 Rec. "F 675 pregnant.

It is, therefore, an object of the instant invention to provide a vapor phase process carried on in the presence of added gas or gases, which yields a reformed petroleum oil characterized by induced toxic properties having at leastlabou 10-20% residual matter above 315 C.

By the expression a reformed petroleum oil as used herein and in the annexed claims is meant a beneficiated petroleum oil having induced toxicity as stemming from, among other things a change in molecular structure which occurs during the practice of the present process. Thus a reformed petroleum oil is a modified; converted and/or transformed oil, and includes an oil reing oils that have substantial residual matters" I above 315 C. or 355 C., we are able by subjecting them to vapor phase reforming conditionsin the presence of added gas or gases to simplify and stabilize the structure whilst providing in the finally beneficiated oil substantial residual materials above 315 C. or 355 C;, at the sametime unveiling the toxic qualities, and if the process is carried to an extent'to provide specific gravities in fractional parts of the beneficiated'material as noted in the following tabular data? Fractions Low limit 7 High limit and'preferably carried to the extent to provide specific gravities in fractional parts of the beneficiated material as noted in the following tabular data:

commercial toxicity is secured. 13y stripping from the beneficiatedmaterialv the excess of fractions boiling below 210 C. as required by commercial specifications, (or specifically whatever other low boiling temperature is specified), we are able to use the residue as a commercial wood preservative impregnant with acceptable toxic properties.

In the event this material has too great a residue at 355 C. orhas too high a coke residue for any particular service the desired preservative .oil may be secured as an extract, distillate orresidue having no excess of the desired materials at 355 C. or an excessfof coke residue. I c

.The following examples wilfillustrate several modes of practicing the process of the instant invention; I a i Example 1.-;-A so-called petroleum aromatic, relatively non-toxic, having substantially no ends boiling below 270 0., materials boiling at about 355 C., specific gravities of 0.9251 and 0.9537 in the fractions 270-315 C. and 315-355" C., respectively, is subjected in the vapor phase to. the action of hydrogen at a temperature of 500 C.

whilst under a pressure of 1,000 pounds for such parts of the beneficiated oila specific gravity fall- 1 ing between the limits noted in the following and preferably for such a length of time as to provide in the fractional parts of thebeneilciated oil a specific gravity falling between the noted in the following tabular data: 1

' Fractions Low limit High limit ere-235 0.... 0. 829 l 0. cm s15-a55 0.... 1.001 1 1.1025

Operating under the conditions above named limits a period selected between. the limits of one and two hours will illustratively serve to provide a percentage of newly induced materials. boiling below 210 C. and specific gravities falling between the preferred limits in the fractional parts of the beneflciated oil noted above.

When the period of treatment has been completed the oil is condensed and inspected and is found to require a smaller concentration for a given growth inhibition of wood destroying fungi (Madison 517) than the parent feed stock to such an extent as to be useful as wood preservative. The induction and/or provision of the specific gravities in the fractional parts of the beneficiat- 'ed oil mentioned above is a valid test for the induction of toxicity in the fractions referred to,

and further is an indication that toxicity has been treatment.

induced. in other. fractions of the material under The overall beneficiated material may b used "as a preservative or for anyother purpose to which toxic oils are pm. If desired, a wood preservative' impregnant complying with specifications extant, or of consumer preference, may be segregated from, the overall beneficia-ted oil as a stabilized residual, distillate or extract, and in the event the extract has non-permissible low boiling ends, the extract may bgstabilizedto the desired extent by removal of low boiling ends.

As illustrative of wood preservative impregnants that are meeting with consumfiracceptance and which may be segregated from the overallbeneiiciated material of the instant process. the following tabular data show several published specifications:

Woon PnEssRvA'nvE Imrancmn'rs Specifications 1. American Wood Preservers Association arUp to 210 C., not more than 5% b. Up to 235? C., not more than 25% 2. American Wood Preservers Association (1. Up to 210 (3., not more than 1% 1). Up to 235.C., not more than 10% r c. Up'to 355 (3., not less than 65% 3. American 'Wood Preservers Association a. Up to 235 0., not more thanl /e bi Up to 500 0., not more than ni /2% c. Up to 355 C., not less than 45% 4. American Wood Preserver's Association a. Up to 210. (3., not more than 8% 5. Up to 235 0., not more than 35% 5. American Wood Preservers Association 1 11. Up to 210 0., not more than 10% b. Up to 235 0., not more than 40% 6. American Wood Preservers Association (1. Up to 210 c.1101; more than 5% b. Up to 235 0.; not more than 15% 7. Prussian Ry.

- 11. Up to 150 0., not more than 3% 1). Up to200 C.', not more than 10% 'c. Up to 235 0.; not more than 25% 8. National Paint, Varnish 8a Lacquer Associa- By the nature of the process it is obvious that modifications of existing specifications or other and more exacting specifications may be met.

As mentionedtin the foregoing the process vasiables are so coordinated as to jointly provide newly formed fractions boiling below 210 C. and a preferred limit of specific gravities in the frac tions 210-235" C. and 315-355 C. of the beneilciated oil. a i

In lieu of jointly controlling the process as to provide the aforenamed specific gravities in the 210-235 C. and 3l5-355 C. fractions of the benef flciated l. thenroper control may b v evidenced i in accor ance with the following example:

Example 2.-Select a. material comparable in chemical analysis and boiling range to the feed stock mentionedin Example 1.' Subject same in vapor'phaseto the action of hydrogen ata temperature of- 505 C. whilst underia pressure. of f 2,000 pounds.

Carry onthe process for'such a length of timeas to jointly providev (1)" newly formed oils boiling be1ow.2l0 C."and.(2) inith'e.

fractions.235- 270 C. and'315-355 C. specific gravities falling. betweenthe limitslnoted below:

Fractions Low-limit I High'liniit ass-270 o- 0.850 1.0315 3l5355 G 0. 973 1.1175

and preferably between thefollowlng'limits:

Fractions Low limit High limit 3l5 355 C i 1.001

At the end ofthe-named treatment'period the. oil is condensed and inspected; and is found to- The :inductionofn have induced toxic properties: the specific gravities in the fractional parts of the beneficiation stated in the present example is a valid test for theinduction of toxicity in the frac- I tions referred to, and further is an indication that toxicity has been induced in other fractions of the material under treatment- Example 3;Select a material. comparable to the feed stock mentioned in Example 1. Subject same in vapor phase to the-action ofv hydrogen at a temperature of 525 C; whilst 'underalpressureof 3,000 pounds. Carry on the process for such a length oftime'as to jointly provide and/or in duce (1) newly formed oilsboilingbelow210 C. and (2) in thefractions 270-315" Cfiand '315-355 C. specific gravities. falling between the limits noted below:

Fractions Low limit High limit 270-315 C 0. 914 1.0691 3l5355 C 0. 973 l. 1175 and preferably between the followinglimits:

Fractions Low limit High limit 270-31 5 C i O. 942 1. 05-11 3l5-355" 0.. 1.001 1.1025

Operating under the conditionsabove named a period selected between the limits of one and two hours will illustratively serveto provide a percentage of newly induced materials boiling below 210 C. and specific gravitiesifalling between the preferred limits in the fractional parts of the beneficiated oil noted above.

When the period of treatment'has been completed the oil is cooled, condensed and inspected; It will be found that the overall beneficiationrequires a smaller concentration for a given growth inhibition of wood destroying fungithan the parent feed stock to such an extent as to be useful as a wood preservative. The induction of the specific gravities in the fractional parts of the 'beneficiated oil mentioned in the instant example C.' and is a valid test for theinduction of toxicity inthe-- fractions referred to, and further'is an indication that toxicity has been induced in'otherfractionsof the materialunder treatment.

Example 4.-Select a petroleum aromaticextract boiling preponderantly above270 C. and: materials boiling at least as high as about355 C.

Subject same in vapor phase to theaction'of hy'-'- drogen at a temperature of 510 C. whilst under a Carry on the processfor such a length oftime as to jointly provide (1) pressure of 1500 pounds.

newly formed oils boiling below 210 C. and (2) in the fraction boiling between 315 C. and 355C. a specific gravity falling between the limits. of 0.973 and 1.1175, and preferably between the limits of 1.001 and 1.1025.

Carrying on'the process under the conditions of the instant example a period of aboutone hour and .15 minutes will illustratively serve to provide a. percentage of newly induced materials boiling below210 C .'and a specific gravity fallingbetween the preferred limits in the 315-'-355 C. fraction of the beneficiation.

At the end of the processing periodtheoil is cooled, condensed and inspected. Find in the beneficiation a toxicity in excess of: that of the parent feed stock. The induction of the specific gravity between the limits stated in the materials boiling between 315 C. and 355 C." is a valid test I for the induction of toxicity in'the fraction referred to; and further is an indication that toxicity has been induced in other fractions of the.

possible of segregation from the beneficiated feed stock of induced toxicity. As for example, an

oil boiling within the carbolineum preservative range, in which instance the segregation would;

have an initial boiling point of about 270 C., the fractions 270-315 C. and 315-355 C. of which; would have specific gravities falling between the limits of 0.914-10691 and 0973-11175, respec-- tively.

Example 5.-Practice the process of Example 1 with a hydrogen containing gas.

Example 6.Practice the process of Example 2' employing'hydrogen derived from carbon monoxide and water as a. reaction product.

Example 7.--Practice the process of Example 3 with carbon dioxide, as for example with a gas of combustion.

Example 8.--Practice the process of Example 4= 2 with a molybdenum oxide catalyst.

Example 11.Practice the process of Example 3 with a chromium oxide catalyst.

' Example 12.Practice the process of Example 4 with a vanadiumoxide catalyst.

, 1 with a tin sulfide catalyst.

Example 18.Practice the process of Example 4 with pelleted Bentonite clay as 2 with the ccprecipitated oxides of copper and chromium as catalytic materials.

Example 19.--Practice the 3 with tin chloride as catalytic material. 1 Example Zn-Practice the process of Example 4 with aluminum chloride as catalytic material.

Example 21.--Practice the process of Example 1 with iodine as catalytic material. H

Example 22.-Practice the process of Example 2 with iodoform as catalytic material.

Example 23.--Practice the process of Example 3 with hydriodic acid as catalytic material.

Example 24.Practice the process of Example 4 with chlorine as catalytic material.

Example 25.--Practice the process of Example 1 with bromine as catalytic material.

' Example 26.-Practice the process of Example 2 with a hydrogen halid as catalytic material.

Example 27.Practice the process of Example 3 with ammonium chloride as catalytic material.

Example 28.--Practice the process of Example catalytic material.

Example 29.-Practice the process of Example 1 with activated Attapulgus clay as catalytic material.

Example 30.Practice the process of Example 2 with a silica hydrogel as catalytic material.

Example 31 .Practice the process of Example 3 with a silica hydrogel impregnated with an aluminum salt as catalytic material.

Example 32.Practice the process of Example 4 with Bentonite and an adsorptive clay as catalytic materials.

Example 33. -Practice the process of Example 1 with a silicious material impregnated with a metallic oxide as catalytic material.

Example 34.Practice the process of Example 2 with a silicious material impregnated with a metallic sulfide as catalytic material.

Example 35.--Practice the process of Example 3 with coprecipitated alumina and chromia hydrogels as catalytic materials.

Example 36.-Practice the process of Example 4 with a synthetic silica-alumina gel as catalytic material.

In the Examples 1-4, inclusive, instances have been cited wherein the starting feed stocks have very small percentages, if any, of material boiling below 270' C. The instant process, as illustrated by Examples 14 inclusive, or others, is adapted to thermally treat in vapor phase in the presence of a protective gas of extraneous source, within the processing limits herein disclosed, a mixture of petroleum fractions characterized by relatively little toxicity, as for example the socalled aromatic extracts, having fractions boiling within the wood preservative range and thereby provide an overall treated oil requiring a smaller concentration for a given growth inhibition of wood destroying fungi than the starting feed stock to such an extent as to be useful as a wood preservative impregnant.

Various purposes appear to be accomplished bythe vapor phase induction of toxicity in the presence of a. gas or gases of extraneous source, above referred to as a protective gas, not accomplished by a liquid phase treatment. Among the purposes accomplished may be mentioned the thermal protection of the material under treatment whereby to preclude or minimize undesirable polymerization, and in the event the gas or gases take part in the reforming action, additional benefits are noted. It has been determined that various gases of extraneous source provide process .of Example these desired and beneficial results in varying degrees. It has specifically been determined that included among these beneficial gases are hydrogen. hydrogen containing gases and substantially inert gases containing carbon. Also specifically employable are carbon dioxide and nitrogen.

The gases above mentioned may be employed separately or in admixture. and this provision, in one mode of operation, is to be specifically read into all examples.

Various catalysts assist in the reforming, transforming, modifying and/or converting of the starting petroleum oils whereby to provide materials of induced toxic properties. Many catalysts other than noted in the foregoing are also employable as effective substances. Viewed broadly, the oxides and sulfides of metals may be used as well as the carbonates and metals themselves. Cellulosic materials and carbo'ii, activated or otherwise may be used with advantage.

Especially effective as catalytic materials are 0xides and sulfides of metals, silicious materials, halids, halogens and derivatives thereof, including specifically substitution and addition products thereof, as for example and specifically substitution and addition products of said derivathe pressures employed. It is, of course, understood'that when relatively low temperatures are employed the lower will be the pressure in order to provide vapor phase operation, and when operating at very low temperatures pressures only slightly above atmospheric will sumce. Temperatures employable are selected between the limits of 400-600 C., and preferably between 425-500 C.

Various pressures are employable as for instance 10, 50, 100 atmospheres or higher, and

these pressures are so coordinated with the temperatures selected as to give total or substantially total vapor phase operation.

If desired instead of subjecting the entirety of the starting feed stock to a single toxicity inducing operation in the vapor phase, the parent material may be segregated into a plurality of cuts and these plurality of cuts separately sub- Jected to separate vapor phase toxicity inducing operations wherein the temperatures in each instance are dissimilar, as for example, but not as a restriction, subjecting the highest boiling cut to the lowest temperature, etc.

The hydrocarbon partial pressure or the partial pressure of the gas or gases employed may vary over wide limits, as for example it may represent a partial pressure of 5-50% or higher.

The time element is specifically selected so as .to provide in the overall beneficiated material newly formed materials boiling below 210 C. and specific gravities in the fractional parts described falling between the stated limits. Using any given feed stock, afew trials will enable those skilled in the art to determine the correct period of treatment.

The process of the instant invention may be practiced in an intermittent processing vessel or in a continuous manner as will become apparent to those skilled in the art after having read the foregoing disclosures.

In the examples shown in the foregoing, one or more phases, etc., of one example may be added to or substituted for other phase or phases in another example where the substitution or addition is obviously workable.

While Examples to 36 disclose the employment of definite catalysts and gases with definite ones of the Examples 1 to 4 inclusive, it, is to be fully understood that these catalysts and gases are interchangeable with the definite controls of the early examples, and any of the named catalysts, gas or gases, or their equivalents are usable in any ofthe Examples 1 to 4 inclusive, and certain toxicity benefits will flow therefrom. The examples given, and the catalyst and gas linked therewith are for the purposes of illustration only.

Minor changes may be made within the scope of the appended claims without departing from the spirit of the invention. In the claims affixed to this specification no selection of any particular modification is intended to the exclusion of other modifications thereof and the right to subsequently make claims to any modification not covered by these claims is expressly reserved.

We claim:

-1. In the induction of toxicity into a mixture of petroleum fractions boiling preponderantly above 270 C., characterized by inherent but inhibited toxicity and a substantial percentage of materials of ring structure content, the process which comprises: subjecting said material in vapor phase to a temperature selected between the limits of 400-600 C. whilst contacting a gas of extraneous source under superatmospheric pressure; unveiling toxicity in the material under treatment by carrying on the process for a time not in excess of about one and one-half hours, the period being so selected with reference to the chosen temperature and pressure as to jointly provide newly formed materials boiling below 210 C. and specific gravities in the fractions 210- 235 C. and 315355 C. of the beneficiated materiaLfalling between the limits of about 0.801- 1.0048 and 0.973-1.1175, respectively; and segregating from the overall beneficiated material an oil of the wood preservative-type characterized by induced toxic properties, boiling preponderantly between 210 C. and 355 C., having at least about -20% residual matter above 315 -C., the fraction 270315 C. of which has an overall specific gravity between 0.914 and 1.0691, and the fraction of which roiling between 315355 C. has an overall specific gravity between 0.973and 1.1175.

2. In the induction of toxicity into a mixture of petroleum fractions boiling preponderantly above 270 C., characterized by inherent but inhibited toxicity and a substantial percentage of materials of ring structure content, the process which comprises: subjecting said material in vapor phase to a temperature selected between the limits of 400-600 C. whilst contacting a gas of extraneous source under superatmospheric pressure; unveiling toxicity in the material under treatment by carrying on the process for a time not in excess of about one and one-half hours, the period being so selected with'reference to the chosen temperature and. pressure as to jointly provide newly formed materials boiling below 210 C. and specific gravities in the fractions 235-270 C. and 315-355 C. of the beneficiated material, falling between the limits of about 0.850-1.0315 and 0973-11175, respectively; and segregating from the overall beneficiated material an oil of the wood preservative type characterized by induced toxic properties, boiling preponderantly between 210 C. and 355 C., having at least about 10-20% residual matter above 315 C., the fraction 270-315 C. of which has an overall specific gravity between 0.914 and 1.0691, and the fraction of which boiling between 315-355 C. has an overall specific gravity between 0.973 and 1.1175.

3. In the induction of toxicity into a mixture of petroleum fractions boiling preponderantly above 270 C., characterized by inherent but inhibited toxicity and a substantial percentage of materials of ring structure content, the process which comprises: subjecting said material in vapor phase to a temperature selected between the limits of 400-600 C. whilst contacting a gas of extraneous source under superatmospheric pressure; unveiling toxicity in the material under treatment by carryingon the process for a time not in excess of about one and one-half hours, the

segregating from the overall beneficiated material an 'oil of the Wood preservative type characterized by induced toxic properties, boiling preponderantly between 210 C. and 355 C., having at least about 10-20% residual matter above 315 C., the fraction 270-315 C. of which has an overall specific gravity between 0.914 and 1.0691, and the fraction of which boiling between 315-355". C. has an overall specific gravity between 0.973 and 1.1175.

4. The process of claim 1 wherein the gas of extraneous source is hydrogen.

5. The process of claim 1 wherein the gas of extraneous source is a hydrogen containing gas.

. 6. The process of claim 1 with inclusion of carrying on the process in the presence of a reforming catalyst.

7. The process of claim 2 with inclusion of carrying on the process in the presence of a reforming catalyst.

8. The process of claim 3 with inclusion of carrying on the process in the presence of a reforming catalyst.

9. The process of claim 1 with inclusion of carrying on the process in the presence of a catalytic material selected from the group consisting of oxides and sulfides of heavy metals.

10. The process of claim 2 with inclusion of carrying on the process in the presence of a catalytic material selected from the group consisting of oxides and sulfides of heavy metals.

11. The process of claim 3 with inclusion of carrying on the process in the presence of a catalytic material selected from the group consisting of oxides and sulfides of heavy metals.

12. The process of claim 1 with inclusion of carrying on the process in the presence of a halogen, halid or derivative thereof, including substitution and addition products thereof, as catalytic material.

13. The process of claim 2 with inclusion of carrying on the process in the presence of a halogen, halid or derivative thereof, including ascaaeo substitution and addition products thereof, as catalytic material.

14. The process or claim 3 with inclusion of carrying on the process in the presence or a halogen, halid or derivative thereof, including substitution and addition products thereof, as catalytic material.

15. The process of claim 1 with inclusion of carrying on the process in the presence of silicious materia1 as catalytic agent.

16. The process of claim 2 with inclusion of carrying on the process in the presence of sill cious material as catalytic agent.

.17. The process of claim 3 with inclusion of carrying on the process in the presence of silicious material as catalytic agent. 1

18. A petroleum derived preservative wood impregnant consisting of in its entirety a mixture of cracked petroleum fractions characterized by a preponderance of materials boiling between 210 C. and 355 C., and at least -20% residual materials boiling above 315 C., the fraction 210- 235 C. of which has an overall specific gravity between 0.801 and 1.0048; the fraction 235-270 C. of which has an overall specific gravity between 0.850 and 1.0315; the fraction 270-3l5 C. of which has an overall specific gravity between 0.914 and 1.0691; and the fraction of which boiling between 315-355 C. has an overall specific gravity between 0.973 and 1.1175.

19. A petroleum derived preservative wood impregnant consisting of in its entirety a mixture of cracked petroleum fractions characterized by a preponderance of materials boiling between 210 C. and 355 C., and at least 10-20% residual materials boiling above 315 C., the fraction 235-270 C. of which has an overall specific gravity between 0.850 and 1.0315; the fraction 270-315" C. of which has an overall specific gravity between 0.914 and 1.0691; and the fraction of which boiling between 3l5-355 C. has an residual materials boiling above 315 C., the fraction 270-315 C. of which an overall specific gravity between 0.914 and 1.0691: and the treetion of which boiling between 315-355 C. has an overall specific gravity between 0.973 and 1.1175, being a dehydrogenated product of petroleum fractions.

21. The. process of inducing toxicity into a petroleum derived material, which comprises:

subjecting a mixture of petroleum fractions boil- 1 one-half hours, the period being so selected with reference to the chosen temperature and pressure as to jointly provide newly formed materials boiling below 210 C., and. an overall beneficiated material containing fractional parts having a specific gravity falling substantially between the limits noted in the appended tabular data:

Fractions Low limit High limit 4 ass-270 C 0.850 1.0315 ave-315 0.... 0. 911 1.0091 315-355 C 0. 973 1.11

whereby to provide a material of induced toxic properties; and segregating from the overall beneficiated material an oil-of the wood preservative type characterized by induced toxic properties, boiling preponderantly between 210 C. and 355 C., having at least about 10-20% residual matter above 315 C., the fraction 270-315? C. of which has an overall specific gravity between 0914 and 1.0691, and the fraction of which boiling between SIS-355 C. has an overall specific gravity between 0.973 and 1.11175.

JACQUELIN E. HARVEY, J11. ROBERT H. .WHITE, J11. JOSEPH A. VAUGHAN. 

